Application of NMR spectroscopy and mass spectrometry to the structural elucidation of modified flavan-3-ols and their coupling reaction products

Spectroscopy Letters

Volumn 41, Issue 2, 2008, Pages 41-56

  Es Safi, Nour Eddine ^a,b   Guernevé, Christine Le ^c   Ducrot, Paul Henri ^a  

^a CEMAGREF   (France)

^b MOHAMMED V UNIVERSITY IN RABAT   (Morocco)

^c SPO   (France)

Author keywords

Characterization; Collision induced dissociation; ESI MS; Flavanols; Fragmentation; HMBC; HSQC; MS MS; NMR; Polyphenols; Procyanidins

Indexed keywords

EID: 42349095069     PISSN: 00387010     EISSN: 15322289     Source Type: Journal    
DOI: 10.1080/00387010801937782     Document Type: Article

References (28)

1. Macheix, J. J.; Fleuriet, A.; Billot, J. Fruit Phenolics; CRC Press: Boca Raton FL, 1990; 378 pp.
2. Ferreira, D.; Bekker, R. Oligomeric proanthocyanidins: Naturally occurring O-heterocycles. Nat. Prod. Rep. 1996, 13, 411-433.
3. Porter, L. J. Flavans and proanthocyanidins. In The Flavonoids: Advances in Research since 1986; Harborne, J. B. Ed.; Chapman and Hall: New York, 1994, 23-54.
4. Ferreira, D.; Nel, R. J. J.; Bekker, R. In Comprehensive Natural Products Chemistry; Barton, D. H. R., Nakanishi, K., Meth-Cohn, O., and Pinto, B. M., Eds.; Elsevier: New York, 1999; Vol. 3, pp. 747-797.
5. Ferreira, D.; Brandt, E. V.; Coetzee, J.; Malan, E. Condensed tannins. In The Chemistry of Organic Natural Products; Zechmeister, L., Herz, W., Falk, H., Kirby, G. W., and Moore, R. E. Eds.; Springer Verlag:Wien, 1999; Vol. 77, 21-67.
6. Ariga, T.; Koshiyama, I.; Fukoshima, D. Antioxidative properties of procyanidin B1 and B3 from azuki beans in aqueous systems. Agric. Biolo. Chem. 1988, 52, 2717-2722.
7. Landrault, N.; Poucheret, P.; Ravel, P.; Gasc, F.; Cros, G.; Teisseidre, P.-L. Antioxidant capacities and phenolics levels of french wines from different varieties and vintages. J. Agric. Food Chem. 2001, 49, 3341-3348.
8. Zhao, J.; Wang, J.; Chen, Y.; Agarwal, R. Anti-tumor-promoting activity of a polyphenolic fraction isolated from grape seeds in the mouse skin two-stage initiation-promotion protocol and identification of procyanidin B5-3′-gallate as the most effective antioxidant constituent. Carcinogenesis 1999, 20, 1737-1745.
9. Balas, L.; Vercauteren, J. Extensive high-resolution reverse 2D NMR analysis for the structural elucidation of procyanidin oligomers. Magn. Reson. Chem. 1994, 32, 386-393.
10. Balas, L.; Vercauteren, J. Extensive high-resolution reverse 2D NMR analysis for the structural elucidation of procyanidin oligomers. Magn. Reson. Chem. 1994, 32, 386-393.
11. Flamini, R. Mass spectrometry in grape and wine chemistry. Part I: Polyphenols. Mass Spectrom. Rev. 2003, 22, 218-250.
12. Beauhaire, J.; Es-Safi, N.; Boyer, F. D.; Kerhoas, L.; Le Guernevé, C.;Ducrot, P. H. Synthesis ofmodified proanthocyanidins: introduction of acyl substituents at C-8 of catechin. Selective synthesis of a C-4 → O → C-3 ether-linked procyanidin-like dimer. Bioorg. Med. Chem. Lett. 2005, 15, 559-562.
13. Boyer, F. D.; Es-Safi, N.; Beauhaire, J.; Le Guernevé, C.; Ducrot, P. H. Synthesis of modified proanthocyanidins: easy and general introduction of a hydroxy group at C-6 of catechin; efficient synthesis of elephantorrhizol. Bioorg. Med. Chem. Lett. 2005, 15, 563-566.
14. Es-Safi, N.; Le Guernevé, C.; Kerhoas, L.; Ducrot, P. H. Influence of an 8-trifluoroacetyl group on flavanol couplings-Tetrahedron 2006, 62, 2705-2714.
15. Steenkamp, J. A.; Ferreira, D.; Roux, D. G. Stereospecific functionalization of the heterocyclic ring systems of flavan-3-OL and [4,8]-biflavan-3-OL derivatives with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ). Tetrahedron Lett. 1985, 26, 3045-3048.
16. Steenkamp, J. A.; Mouton, C. H. L.; Ferreira, D. Regio- and stereoselective oxidation of flavan-3-ol-4-arylflavan-3-ol-and biflavanoid derivatives with 2,3-dichloro-56-dicyano-1,4-benzoquinone (DDQ). Tetrahedron 1991, 47, 6705-6716.
17. Es-Safi, N.; Ducrot, P. H. Oxidation of flavan-3-ols: gram-scale synthesis of taxifolin. Lett. Organic Chem. 2006, 3, 231-234.
18. Tückmantel, W.; Kozikowski, A. P.; Romanczyk, L. J., Jr. Studies in polyphenol chemistry and bioactivity. 1. preparation of building blocks from (+)-catechin. procyanidin formation. Synthesis of the cancer cell growth inhibitor, 3-O-galloyl-(2R,3R)-epicatechin-4b,8-[3-O-galloyl-(2R,3R)- epicatechin]. J. Ame. Chem. Soc. 1999, 121, 12073-12081.
19. Saito, A.; Nakajima, N.; Tanaka, A.; Ubukata, M. Synthetic studies of proanthocyanidins. Part 2: Stereoselective gram-scale synthesis of procyanidin-B3. Tetrahedron 2002, 39, 7829-7837.
20. Kawamoto, H.; Nakatsubo, F.; Murakami, K. Synthesis of condensed tannin derivatives regiosepecifically linked through a single interflavanoid-linkage and their protein-precipitating capacities. Mokuzai Gakkaishi 1991, 37, 488-493.
21. Yoneda, S.; Kawamoto, H.; Nakatsubo, J.; Yoneda, S.; Kawamoto, H.; Nakatsubo, F. Synthesis of high molecular mass condensed tannin by cationic polymerization of flavan 3,4 carbonate. J. Chem. Soc. Perkin Trans. 1997, 1, 1025-1030.
22. Steinberg, P. J.; Nel, R. J. J.; Van Rensburg, H.; Bezuidenhoudt, B. C. B.; Ferreira, D. Oligomeric flavanoids. Part 27. Interflavanyl bond formation in procyanidins under neutral conditions. Tetrahedron 1998, 54, 8153-8158.
23. 13C-labelled (-)-procyanidin B3. Tetrahedron Lett. 2001, 42, 5669-5671.
24. 13C]-acetic acid. Tetrahedron Lett. 2001, 42, 1279-1281.
25. Delcour, J. A.; Ferreira, D.; Roux, D. G. Synthesis of condensed tannins part 9. The condensation sequence of leucocyanidin with (+)-catechin and with the resultant procyanidins. J. Chem. Soc. Perkin Trans. 1983, 1, 1711-1717.
26. Bennie, L.; Coetzee, J.; Malan, E.; Woolfrey, J. R.; Ferreira, D. Oligomeric flavanoids. Part 34: Doubly-linked proteracacinidin analogues from Acacia caffra and Acacia galpinii. Tetrahedron 2001, 57, 661-667.
27. Salas, E.; Atanasova, V.; Poncet-Legrand, C.; Meudec, E.; Mazauric, J.; Cheynier, V. Demonstration of the occurrence of flavanol-anthocyanin adducts in wine and in model solutions. Anal. Chim. Acta 2004, 513, 325-332.
28. Boyer, F.; Ducrot, P. H. Hydrogenation of substituted aromatic aldehydes: nucleophilic trapping of the reaction intermediate, application to the efficient synthesis of methylene linked flavanol dimers. Tetrahedron Lett. 2005, 46, 5177-5180